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Peer-reviewedCC BY-NC 3.0Dalton Transactions (Cambridge, England : 2003)

Probing the electronic origins of heterometallic tuning in platinum complexes by 195Pt NMR spectroscopy

  • Riddhi R. Golwankar1
  • Alexander C. Ervin1
  • Soumya Ranjan Dash2
  • Emily R. Mikeska1
  • Justin T. Douglas3
  • Jochen Autschbach2
  • James D. Blakemore1
  1. 1Department of Chemistry, University of Kansas 1567 Irving Hill Road Lawrence Kansas 66045 USA
  2. 2Department of Chemistry, University at Buffalo, State University of New York Buffalo NY 14260 USA
  3. 3Nuclear Magnetic Resonance Laboratory, Molecular Structures Group, University of Kansas Lawrence Kansas 66047 USA
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Abstract

Incorporation of secondary, effectively Lewis acidic metal cations into heterometallic complexes is a useful strategy for tuning chemical properties and reactivity, but addressing the origins of metal-driven tunability and quantitative correlation of metal-focused data with computational modeling have not received the attention they deserve. Here, the synthesis and characterization of a series of diamagnetic complexes containing platinum(ii) and secondary cations (K+, Sr2+, and Lu3+) are reported, along with nuclear magnetic resonance (NMR) measurements of 195Pt chemical shifts (δ195Pt). Similar to related species, the spectroscopic and electrochemical properties of the complexes depend on the Lewis acidity, or charge density, of the secondary cations; the change in δ195Pt was found to be particularly well correlated with Lewis acidity and was therefore studied in detail. Computational investigations of the 195Pt NMR data reveal that the secondary cations induce changes in electron donation to platinum from bridging phenoxide moieties that lead to the experimental chemical shifts. In sum, the results both (i) establish a quantitative model for understanding cation-driven tuning in complexes of this type as well as (ii) demonstrate the usefulness of 195Pt NMR as tool for studying Pt-heterometallic compounds.

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Cite

BibTeXRIS
BibTeX
@article{golwankar2026probing,
  title = {{Probing the electronic origins of heterometallic tuning in platinum complexes by 195Pt NMR spectroscopy}},
  author = {Riddhi R. Golwankar and Alexander C. Ervin and Soumya Ranjan Dash and Emily R. Mikeska and Justin T. Douglas and Jochen Autschbach and James D. Blakemore},
  journal = {Dalton Transactions (Cambridge, England : 2003)},
  year = {2026},
  month = aug,
  doi = {10.1039/d6dt01469k},
  url = {https://doi.org/10.1039/d6dt01469k},
  note = {CC BY-NC 3.0},
}
RIS
TY  - JOUR
TI  - Probing the electronic origins of heterometallic tuning in platinum complexes by 195Pt NMR spectroscopy
AU  - Riddhi R. Golwankar
AU  - Alexander C. Ervin
AU  - Soumya Ranjan Dash
AU  - Emily R. Mikeska
AU  - Justin T. Douglas
AU  - Jochen Autschbach
AU  - James D. Blakemore
PY  - 2026
DA  - 2026/08/12
JO  - Dalton Transactions (Cambridge, England : 2003)
DO  - 10.1039/d6dt01469k
UR  - https://doi.org/10.1039/d6dt01469k
AB  - Incorporation of secondary, effectively Lewis acidic metal cations into heterometallic complexes is a useful strategy for tuning chemical properties and reactivity, but addressing the origins of metal-driven tunability and quantitative correlation of metal-focused data with computational modeling have not received the attention they deserve. Here, the synthesis and characterization of a series of diamagnetic complexes containing platinum(ii) and secondary cations (K+, Sr2+, and Lu3+) are reported, along with nuclear magnetic resonance (NMR) measurements of 195Pt chemical shifts (δ195Pt). Similar to related species, the spectroscopic and electrochemical properties of the complexes depend on the Lewis acidity, or charge density, of the secondary cations; the change in δ195Pt was found to be particularly well correlated with Lewis acidity and was therefore studied in detail. Computational investigations of the 195Pt NMR data reveal that the secondary cations induce changes in electron donation to platinum from bridging phenoxide moieties that lead to the experimental chemical shifts. In sum, the results both (i) establish a quantitative model for understanding cation-driven tuning in complexes of this type as well as (ii) demonstrate the usefulness of 195Pt NMR as tool for studying Pt-heterometallic compounds.
SN  - 1477-9226
SN  - 1477-9234
ER  -